CN106883115A

CN106883115A - The method that one kettle way prepares adipic acid by cyclopentanone

Info

Publication number: CN106883115A
Application number: CN201510930161.5A
Authority: CN
Inventors: 刘菲; 王爱琴; 张涛
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2015-12-15
Filing date: 2015-12-15
Publication date: 2017-06-23
Anticipated expiration: 2035-12-15
Also published as: CN106883115B

Abstract

The method for preparing adipic acid by cyclopentanone the invention discloses one kettle way.Comprise the following steps：1) using methyl formate (or Ethyl formate) as carbon source, cyclopentanone carries out condensation reaction with methyl formate under the catalytic action of base catalyst, catalysate intermediate (2- oxygen cyclopenta formaldehyde) is obtained, acid is neutralized after reaction terminates, be not required to product Intermediate separation；2) to step 1) product Intermediate solution directly instills aqueous hydrogen peroxide solution carries out oxidative cleavage, and reaction cools down centrifugation after terminating, and obtains rough adipic acid.The present invention has economy and Environmental costs low；Product is easily separated, and post processing is simple to wait remarkable advantage, with good application prospect.

Description

The method that one kettle way prepares adipic acid by cyclopentanone

Technical field

The present invention relates to using methyl formate (or Ethyl formate) as carbon source, in a mild condition, Separated without product Intermediate, the method that one kettle way is prepared adipic acid by cyclopentanone.

Background introduction：

Adipic acid is a kind of important industrial chemicals.Mainly for the production of nylon66 fiber polyester, gather Ester polyol, plasticizer etc..The industrial process of current adipic acid is mainly hexamethylene method, Hexamethylene is produced by purified petroleum benzin catalytic hydrogenation, then cyclohexanone and cyclohexanol are produced through air oxidation, most By nitric acid oxidation synthesizing adipic acid.Other cyclohexene oxide method and butadiene process prepare adipic acid It is also the emphasis of current industrial development.Therefore it is not difficult to find out, adipic acid reparation technology is used mostly Petroleum path.But petroleum resources increasingly depleted, will certainly cause the critical shortage of chemical products, In order to reduce the dependence to petroleum resources, it is that chemical industry can to develop reproducible biomass resource The only way which must be passed of sustainable development.But find a simple and effective approach using biomass resource Remove synthesizing adipic acid not a duck soup.In recent years, researcher had found to be provided using cheap biomass Source furfural can with high selectivity be prepared with high yield cyclopentanone (Patent No. CN103111299, 102875334、103159606、102807483).And it is industrial main using adipic acid decarboxylation Cyclisation method prepares cyclopentanone.Therefore renewable resource → cyclopentanone → adipic acid → cyclopentanone is realized The production technology that product is recycled, not only the target from chemical industry sustainable development is closer to one Step, also for propulsion bio-based materials industry development is laid a good foundation.

The content of the invention

It is an object of the invention to cyclopentanone as raw material, methyl formate (or Ethyl formate) is Carbon source, first alkaline condensation reoxidizes open loop under the catalytic action of catalyst, finally obtains rough Adipic acid.The present invention is single for the raw material sources of current industrially prepared adipic acid, accessory substance Binary acid is more, the problems such as poor selectivity, proposes a kind of to prepare the new of adipic acid by cyclopentanone Approach.

To achieve the above object, the present invention uses following technical scheme:

1) under solvent or condition of no solvent, the one kind in cyclopentanone and methyl formate or Ethyl formate Or two kinds there is condensation reaction under the catalytic action of base catalyst, reaction terminate after with acidity Solution is neutralized, and obtains product Intermediate solution；

2) directly aqueous hydrogen peroxide solution is passed through product Intermediate solution in agitating heating for a period of time Rough adipic acid can be obtained.

In step 1) in, the base catalyst is sodium methoxide, potassium methoxide, the ethanol in solid base One or two or more kinds of sodium, sodium tert-butoxide or potassium tert-butoxide；It is described have a solvent condition under, it is molten Agent is one or two or more kinds in methyl alcohol, ethanol or tetrahydrofuran；The acid is hydrochloric acid, nitre Acid or sulfuric acid in one or two or more kinds；The consumption of the cyclopentanone is in the case where there is solvent condition The 1%-50% of solution quality, preferably 5-25%；Under condition of no solvent, cyclopentanone consumption with The mass ratio of formic acid carbon source consumption is 1：1 to 1：10, preferably 1：2 to 1：5；The first The consumption of sour methyl esters is the 5%-99%, preferably 25-90% of solution quality in the case where there is solvent condition； Cyclopentanone is 1 with base catalyst mass ratio:0.5 to 1:2, preferably 1:0.8 to 1:1.5；Instead Answer temperature at 0 DEG C -80 DEG C, preferable reaction temperature is at 30 DEG C -50 DEG C；Reaction time 1h-24h, Preferred reaction time is in 5h-12h；Reaction is neutralized to pH value of solution for 5-6 after terminating.

In step 2) in, the mass concentration of the aqueous hydrogen peroxide solution is 30wt% (commercially), The mass fraction of aqueous hydrogen peroxide solution consumption is 2-3 times of cyclopentanone consumption；Reaction temperature exists 0 DEG C -80 DEG C, preferable reaction temperature is at 30 DEG C -50 DEG C；Reaction time 0.1h-12h, preferably instead In 0.5h-5h between seasonable.

Step 2) react and terminate rear cooled reaction solution until having Precipitation, centrifugation. Another method is to remove part moisture, then cooled reaction solution with revolving instrument after the completion of reaction Until there is Precipitation, centrifugation obtains rough adipic acid..

Advantageous Effects：

The method that " one kettle way " of the invention prepares adipic acid by cyclopentanone, optimal anti- Under the conditions of answering, rough adipic acid yield can reach 90%.The method have it is simple to operate safety, The remarkable advantage such as Atom economy is high, recovery is easy, product is easily separated；It is that there is work higher The environmental protection route of industry prospect, in technology and economic aspect all very advantageous.

Specific embodiment

With reference to specific embodiment, the present invention will be described in detail, the description of this part Only it is exemplary and explanatory, there should not be any limitation to make to protection scope of the present invention With.

Embodiment 1

By the ethanol solution (amount of alcohol is 5mL) of 0.25g cyclopentanone and 0.45g methyl formates In addition 25mL round-bottomed flasks, while adding 0.2g sodium methoxides to stir 3 at 40 DEG C to flask Hour, add the aqueous hydrochloric acid solution that mass concentration is 10% to neutralize after stopping reaction, until instead It is in acid (pH is 5) to answer solution.The aqueous hydrogen peroxide solution 1mL of 30wt% is subsequently adding, Reaction solution intensification is heated into 40 DEG C after stirring to react 5 hours, reaction is cooled down after terminating, By excessive methyl formate, rotary evaporation falls under conditions of 30 DEG C/20mmHg, and rough oneself two Acid is deposited in bottom of bottle, and centrifugation must precipitate (rough adipic acid), and yield is 90%.

Embodiment 2

Cyclopentanone 0.5g and methyl formate 2.5g is added in 25mL round-bottomed flasks, while adding to flask The methanol solution (quantity of methyl alcohol is 5mL) for entering 0.4g sodium methoxides is stirred at room temperature 10 hours, The aqueous hydrochloric acid solution that mass concentration is 10% is added to neutralize after stopping reaction, until reaction solution In acid (pH is 6).The aqueous hydrogen peroxide solution 2mL of 30wt% is subsequently adding, stirring is equal Reaction solution intensification is heated into 40 DEG C after even to react 5 hours, reaction is cooled down after terminating, incited somebody to action The methyl formate of amount rotary evaporation under conditions of 30 DEG C/20mmHg falls, and rough adipic acid sinks Form sediment in bottom of bottle, centrifugation must precipitate (rough adipic acid), and yield is 80%.

Embodiment 3

During 0.25g cyclopentanone and 0.45g methyl formates added into 25mL round-bottomed flasks, while to burning Bottle adds 0.2g sodium methoxides to be stirred 5 hours at 40 DEG C, and mass concentration is added after stopping reaction Aqueous hydrochloric acid solution for 10% is neutralized, until reaction solution is in acid (pH is 5).Then plus Enter the aqueous hydrogen peroxide solution 1mL of 30wt%, reaction solution heats up after stirring be heated to 40 DEG C are reacted 5 hours, and reaction is cooled down after terminating, by excessive methyl formate in 30 DEG C/20mmHg Under conditions of rotary evaporation fall, rough adipic acid is deposited in bottom of bottle, and centrifugation must precipitate (thick Adipic acid processed), yield is 35%.

Embodiment 4

By the tetrahydrofuran solution of 0.25g cyclopentanone and 0.45g methyl formates, (tetrahydrofuran consumption is 5mL) in addition 25mL round-bottomed flasks, while adding 0.3g potassium tert-butoxides at 40 DEG C to flask Lower stirring 12 hours, in stopping adding mass concentration to be 10% aqueous hydrochloric acid solution after reaction With until reaction solution is in acid (pH is 6).It is subsequently adding the aquae hydrogenii dioxidi of 30wt% Solution 1mL, is heated to 40 DEG C and reacts 5 hours after stirring by reaction solution intensification, reaction knot Cooled down after beam, by excessive methyl formate, rotary evaporation falls under conditions of 30 DEG C/20mmHg, Rough adipic acid is deposited in bottom of bottle, and centrifugation must precipitate (rough adipic acid), and yield is 40%.

Claims

1. the method that one kettle way prepares adipic acid by cyclopentanone, it is characterised in that:

1) in the case where having solvent or condition of no solvent, in cyclopentanone and methyl formate or Ethyl formate One kind or two kinds under the catalytic action of base catalyst occur condensation reaction generation products Intermediate, reaction is neutralized after terminating with acid；

2) aqueous hydrogen peroxide solution is directly passed through above-mentioned steps 1) in the product that finally gives Between in liquid solution agitating heating for a period of time, obtain rough adipic acid.

2. in accordance with the method for claim 1, it is characterised in that:In step 1) in, the alkali Property catalyst be sodium methoxide, caustic alcohol, one kind of sodium tert-butoxide or potassium tert-butoxide in solid base Or more than two kinds；The solvent is one or two or more kinds in methyl alcohol, ethanol or tetrahydrofuran； The acid of the neutralization is one or two or more kinds in hydrochloric acid, nitric acid or sulfuric acid.

3. in accordance with the method for claim 1, it is characterised in that:The consumption of the cyclopentanone is having It is the 1%-50%, preferably 5-25% of solution quality under solvent condition；Under condition of no solvent, The quality of one kind or two kinds of total consumption in cyclopentanone consumption and methyl formate or Ethyl formate Than being 1：1 to 1：10, preferably 1：2 to 1：5；The methyl formate or Ethyl formate In one kind or two kinds of total consumption in the case where there is solvent condition for solution quality 5%-99%, It is preferred that 25-90%；Cyclopentanone is 1 with base catalyst mass ratio:0.5 to 1:2, preferably 1:0.8 To 1:1.5；, at 0 DEG C -80 DEG C, preferable reaction temperature is at 30 DEG C -50 DEG C for reaction temperature；Reaction Time 1h-24h, preferred reaction time is in 2h-12h；Reaction is neutralized to pH value of solution after terminating Between 5-6.

4. in accordance with the method for claim 1, it is characterised in that:In step 2) in, the mistake The mass concentration for aoxidizing aqueous solution of hydrogen is 30wt%, and the quality of aqueous hydrogen peroxide solution is ring penta 2-3 times of ketone quality；, at 0 DEG C -80 DEG C, preferable reaction temperature is at 30 DEG C -50 DEG C for reaction temperature； Reaction time 0.1h-12h, preferred reaction time is in 0.5h-5h.

5. according to the method described in claim 1 or 4, it is characterised in that:Step 2) react and terminate Cooled reaction solution is until have Precipitation, centrifugation afterwards；Or, reaction uses revolving after terminating Instrument removes part moisture, then cooled reaction solution until having Precipitation, centrifugation obtains rough Adipic acid.